Chief executive TomAlbanese stepped down by mutual agreement with the board, Rio Tinto said, and has been replaced by Sam Walsh, chief executive of the miner's iron ore business.
"We are taking further tough action to roll back the unsustainable cost increases of the past few years and are maintaining a relentless focus on improving productivity, " said TomAlbanese, chief executive of Rio Tinto.
The deal digs Mr Albanese out of a hole the size of Tom Price, the huge iron-ore complex in the Pilbara region of Western Australia in which Chinalco stands to take a stake.